Water-insoluble azo-dyestuffs



Patented Sept. 22, 1936 UNITED STATES PATENT OFFICE WATER-VINSOLUBLE AZO-DYESTUFFS Grald Bonhote and Jakob Danuser, Basel, Switzerland, assignors to the firm Society of Chemical Industry in Basle, Basel, Switzerland No Drawing. Application January 17, 1935, Serial No. 2,302. In Switzerland October 13, 1934 8 Claims. (Cl. 260-81) It has been found that new and valuable azodyestufis insoluble in water are obtained by causing diazo-compounds of the general formula in which R1 and R2 represent aromatic nuclei of the benzene or naphthalene series, and in which at least one of the two nuclei R1 and R2 is substituted by an alkoxy-group in ortho-position to the -'-N='N-group,'t o react with 3-hydroxy-7,2- benzofluorenone of the general formula in which one X represents hydrogen and the other X halogen or hydrogen. Particularly valuable results are obtained with products having such alkoxy groups which contain themselves not moreth'an two carbon atoms.

7 The dyestuffs obtainable according to this new process correspond to the general formula treatment with reducing agents, on the one hand, into a compound of the probable general formula wherein the two letters X have the signification indicated above, which product is soluble in alkalies to a violet solution, and, on the other hand, into a mixture consisting of an unsulfonated pri mary amine and an unsulfonated primary aromatic diamine.

The following examples illustrate the invention, without, however, limiting the same:-

Example 1 27.6 parts by weight of 4'-chloro-4-amino-3- methoxy-B-methyl-azobenzene are diazotized as usual and the diazo-solution is introduced into one of 24.6 parts by weight of 3-hydroxy-l,2-benzofluorenone, 50 parts of caustic soda solution of 30 per cent. strength, and 30 parts of calcined sodium carbonate in 2000 parts of water. The dyestuff is precipitated immediately; the black pre- 'cipitate is filtered and dried. It corresponds very probably with the formula and dyes cotton, when produced on this fiber, deep greenish-black tints.

It forms a black powder soluble in pyridine to an olive-green and in sulfuric acid to a blue-' green solution and by reduction yields 1,4-diamino-2-methyl-5-methoxybenzene, 4-chloro-1- aminobenzene and a product soluble in a sodium hydroxide solution with a violet coloration which product corresponds very probably with the mula for- 7 also be used, such as OCHz-CHz--OCH3 or OCH2CH2OCH2CH3.

Similar dyestuffs are formed when using 3-hydroxy-G-chloro 1,2 benzofluorenone or 3-hydroxy-S-chloro-1,2-benzofluorenone instead of 3- hydroxy-1,2-benzofluorenone.

Example 2 Cotton yarn is impregnated with a grounding made by dissolving 10 grams of 3-hydroxy-1,2- benzofluorenone in 300 cc. of hot water with addition of 18 cc. of a sodium hydroxide solution of 30 per cent. strength and 10 cc. of Turkey red oil, and diluting the whole to one liter with addition of 15 grams of common salt. The yarn is then wrung out and developed in a diazo-solution neutralizedwith sodium acetate corresponding to acontent of 3 grams of diazotized 4-amino-2- niethyl5- methoxy-4'-chloro-1,1'-azobenzene per liter. 'Ihere'is produced a full black of very good fastness properties.

' Example 3 Cotton yarn is impregnated with a grounding made by dissolving'lO' grams of 3-hydroxy-1,2- benzofiuorenone. in 300 cc. of hot water with addition of 18' cc. of a sodium hydroxide solution of 30 per cent. strength and 10 cc. of Turkey red oil, and diluting the whole to one liter with addition of 15 grams of common salt. The yarn then wrung out and developed in a diazo-solution neutralized with sodium acetate corresponding'to a content of 3 grams of 4-diazonaphthalen'e-Ll, azo-2'-ethoxybenzene per liter. There is produced a full black of very good fastness properties. The new dyestufi very probably corresponds to the formula It forms a black powder soluble in pyridine to an oliveegreen and in sulfuric acid to a bluegreen solution and by reduction yields 1,4-diamino-naphthalene, 2-ethoxy- 1 -aminobenzene and a product soluble in a sodium hydroxide solution with a violet coloration which product corresponds very probably with the formula A similar black tint is obtained with the 4-d1- azo-naphthalene 1,1 azo-2'-methoxybenzene. The dyestufis prepared with these diazo-compounds correspond very probably with the general formula in which :2: stands for ethyl or methyl. They form black powders, soluble in pyridine to an olive-green and in sulfuric acid to a blue-black solution and by reduction yield 1,4-diaminonaphthalene, 1-amino-2-ethoxy or methoxy-benzene and a product soluble in a sodium hydroxide solution with a violentcoloration, which product corresponds very probably with the formula The dyestufis of the present example can also be produced in the form of pigments as described in Example 1. Similar dyestuffs are also formed here if the diazotizing component contains a higher alkyl radical, or if there are used 3-hydroxy-6-chloroor 3-hydroxy-8-chloro-l,2-benzofluorenone instead of 3-hydroxy-1,2-benzofluorenone.

Example 4 H (I) 02H:

It'formsa'black powder 'soluble'inpyridine to a green and in sulfuric acid. to a blue-violet solutionr and by reduction'yields l,4-diamino-2,5-diethoxybenzene, 31-amino-3-methylbenzeneand a product soluble in a sodium hydroxide solution with awiolet coloration which product corresponds probably with the formula The" dyestuffs of the preceding examples can also be produced on the fiber according to the data of this example.

What we claim =is;-

1. The dyestuffs of the general formula wherein R1 and 32 represent aromatic radicals least-one'bears analkoxy group in ortho-position to .the-N'=N-group, one X stands for hydrogen and the other X for hydrogen or halogen, which dyestuffs are dark powders soluble in pyridine to olive-green to dark-gree'n'solutions, and in sulfuric acid to blue-violet to blue-green and blueblack solutions, and which dyestuffs when produced on the fiber, dye the same tints which are very fast, particularly surprisingly fast to light, and are split by treatment with reducing agents, on the one hand, into a compound of the probable general formula wherein the two letters X'have thesignification 0 indicated above, which product is soluble in alkalies to a violet solution, and, onthe other hand, into a mixture consisting of an unsulfonated primary amine and an unsulfonated primary aromatic diamine. J 2. The dyestuffs of the general formula O-alkyl of the benzene or naphthalene series of which at which are black powders soluble in pyridine to olive-green solutions and in sulfuric acid to bluegreen solutions, which dyestuffs, when produced on the fiber, dye the same black tints which are fast, particularly surprisingly fast to light, and are split by treatment with reducing agents, on the one hand, into a compound of the probable formula soluble in alkalies to a violet solution and, on the other hand, into a mixture consisting of parahalogen-aniline and 1,4-diamino-2-mcthyl-5-alkoxybenzene.

3. The dyestuffs of the general formula OH O-alkyl soluble in alkalies to a violet solution and, on the other hand, into a mixture consisting of paraha1ogenaniline and 1,4-diamino-2-methyl-5-alkoxybenzene. j

4. The dyestuffs of the general formula wherein alkyl represents methyl or ethyl, which dyestuffs are black powders soluble in pyridine to olive-green solutions and in sulfuric acid to bluegreen solutions, and when produced on the fiber, dye the same black tints which are fast, particularly surprisingly fast to light, and are split by treatment with reducing agents, on the one hand, into a compound of the probable formula fast, particularly surprisingly fast to light, and is soluble in alkalies to a violet solution and, on the other hand, into a mixture consisting of parachloraniline and 1,4-diamino-2-methy1-5-a1koxybenzene. a

5. The dyestuif of the formula OCH:

which is a black powdersoluble in pyridine to an, olive-green solution and in sulfuric acid to a blue-- green solution, which dyestuff, when produced on the fiber, dyes the same black tints, which are split by treatment with reducing agents, on the one hand, into a compound of the probable formula soluble in alkalies to aviolet solution and, on the other hand, into a mixture consisting of parachloraniline and 1,4 diamino 2 methyl 5 methoxybenzene.

6. The dyestuffs of the general formula which are black powders soluble in pyridine to olive-green solutions and in sulfuric acid to blueblack solutions, which dyestuffs, when produced on the fiber, dye the same black tints, which are fast, particularly surprisingly fast to light, and are split by treatment with reducing agents, on the one hand, into a compound'of the probable formula 0H soluble'i'n alkalies'to a violet solutlon and, on' the" other hand, into a mixture consisting of l-amino- 2-alkoxybenzene and 1,4-diamino-naphthalene.

7. The dyestuffs of'the general formula.

wherein alkyl represents methyl or ethyl, which dyestuffs are black powders soluble in pyridine to olive-green solutions and in sulfuric acid to blue-black solutions, and, when produced on the fiber, dye the same black tints, which are fast, particularly surprisingly fast to light, and are split by treatment with reducing agents, on the one hand,'into a compound of the probable formula soluble in alkalies toa violet solution and, on the other-hand, into a mixture consisting of l-aminoz-alkoxybenzene :and IA-diamino-naphthaIene.

8. The dyestuff of theformula OCsHs soluble in alkali es to a violet solution and, on the other hand, into a mixture consisting of orthophenetidine and 1,4-diamino-naphthalene.

. V GERALD BON I-IOTE. JAKOB DANUSER. 

